JPWO2009084418A1 - Polyaniline composite, composition thereof and molded product - Google Patents

Abstract

An electrically conductive polyaniline composition comprising an organic solvent, an organic acid, a substituted or unsubstituted polyaniline complex doped with an inorganic acid, and a compound having a phenolic hydroxyl group, wherein the organic acid and inorganic in the polyaniline complex The sum (a) of the acid doping rates is 0.4 <a <0.6, and the ratio (b / a) of the inorganic acid doping rate (b) is 0. A conductive polyaniline composition having a weight average molecular weight of 20,000 or more and a molecular weight distribution of less than 5.0.

Description

  The present invention relates to a novel polyaniline composite and a method for producing the same, and further relates to a conductive composition using the polyaniline composite and a molded product obtained therefrom.

  Polyaniline is a well-known material as one of conductive polymers. In addition to its electrical properties, polyaniline has the advantage and property of being able to be synthesized relatively easily from inexpensive aniline and exhibiting excellent stability against air or the like in a state of conductivity.

As a method for producing polyaniline, a method of electrolytic oxidation polymerization or chemical oxidation polymerization of aniline or aniline derivatives is known.
In electrolytic oxidation polymerization, a film having excellent electrical properties can be obtained. However, in general, the production cost is higher than chemical oxidation polymerization, and it is not suitable for mass production. Have difficulty.

  On the other hand, in order to obtain a conductive aniline or aniline derivative polymer by chemical oxidative polymerization, in general, a dopant (doping agent) is added to polyaniline obtained in a non-conductive base state (so-called emeraldine base state). The process of nation is required. However, polyaniline in the non-conductive base state is not suitable for industrial production because it hardly dissolves in most organic solvents. Furthermore, the conductive polyaniline (so-called emeraldine salt state) generated after the protonation is substantially insoluble and infusible, and it is difficult to easily manufacture a conductive composite material and a molded body thereof.

In response to the above problems, the present inventors have developed a soluble conductive polyaniline complex and a composition thereof that are easy to manufacture and handle (Patent Document 1).
International Publication No. 2005/052058 Pamphlet

  Although the polyaniline complex and the composition thereof described in Patent Document 1 have excellent properties, further improvements have been required for the polyaniline complex and the composition thereof, and the production method thereof.

  Accordingly, an object of the present invention is to provide a novel and excellent polyaniline complex, a method for producing the same, a composition and a molded body using the same.

  As a result of intensive studies, the present inventors have found that the conductivity of the polyaniline composition depends on the organic acid and inorganic acid doping ratio of the polyaniline complex, and the ratio of the organic dopant to the inorganic dopant, the molecular weight, and the molecular weight distribution. Further, it has been found that according to the multistage polymerization method, the polyaniline composite having high conductivity can be obtained by controlling the doping rate, the ratio of the organic dopant to the inorganic dopant, the molecular weight, and the molecular weight distribution within a certain range. In a conductive polymer, the doping rate, doping species, molecular weight, and molecular weight distribution listed here are important structural factors that determine the performance. That is, the polyaniline complex disclosed in the present invention is a novel substance in that it has a characteristic structure factor. According to the present invention, the following polyaniline complex and its composition are provided.

1. An organic solvent, an organic acid, a substituted or unsubstituted polyaniline complex doped with an inorganic acid, and
A conductive polyaniline composition comprising a compound having a phenolic hydroxyl group,
The sum (a) of the organic acid and inorganic acid doping rates in the polyaniline composite is 0.4 <a <0.6,
Of the total doping rate (a), the proportion (b / a) of the doping rate (b) of the inorganic acid is 0.02 or more,
A conductive polyaniline composition wherein the polyaniline complex has a weight average molecular weight of 20,000 or more and a molecular weight distribution of less than 5.0.
2. 2. The conductive polyaniline composition according to 1, wherein a molar concentration of the compound having a phenolic hydroxyl group with respect to 1 g of the polyaniline complex is in a range of 0.01 mmol / g to 50 mmol / g.
3. The organic acid is represented by the following formula (I)
HXARn (I)
{In the formula, X is an acidic group, A is a hydrocarbon group which may contain a substituent, and R is independently -R ¹ , -OR ¹ , -COR ¹ , -COOR ^1. , —CO (COR ¹ ), or —CO (COOR ¹ ) [wherein R ¹ is a hydrocarbon group, silyl group, — (R ² O) x -R which may contain a substituent having 4 or more carbon atoms. ³ groups or-(OSiR ³ ₂ ) x -OR ³ groups (R ² is an alkylene group, R ³ is a hydrocarbon group which may be the same or different, and x is an integer of 1 or more). And n is an integer greater than or equal to 2}
The conductive polyaniline composition according to 1 or 2, which is an organic protonic acid represented by the formula:
4). The organic protonic acid represented by the formula (I) is represented by the following formula (II)
HXCR ⁴ (CR ⁵ ₂ COOR ⁶ ) COOR ⁷ (II)
{In the formula, X is an acidic group, R ⁴ and R ⁵ are each independently a hydrogen atom, a hydrocarbon group or an R ⁸ ₃ Si- group (wherein R ⁸ is a hydrocarbon group, Three R ⁸ may be the same or different, and R ⁶ and R ⁷ are each independently a hydrocarbon group or a — (R ⁹ O) _q —R ¹⁰ group [where R ⁹ is carbon A hydrogen group or a silylene group, R ¹⁰ is a hydrogen atom, a hydrocarbon group or R ¹¹ ₃ Si— (R ¹¹ is a hydrocarbon group, and three R ¹¹ may be the same or different); q is an integer greater than or equal to 1]}
4. The conductive polyaniline composition according to 3, which is an organic protonic acid represented by
5. The organic protonic acid represented by the formula (II) is represented by the following formula (III)
HO ₃ SCH (CH ₂ COOR ¹² ) COOR ¹³ (III)
{Wherein R ¹² and R ¹³ are each independently a hydrocarbon group or — (R ¹⁴ O) _r —R ¹⁵ group [wherein R ¹⁴ is a hydrocarbon group or a silylene group, and R ¹⁵ is hydrogen An atom, a hydrocarbon group, or an R ¹⁶ ₃ Si— group (where R ¹⁶ is a hydrocarbon group, and three R ¹⁶ may be the same or different), and r is an integer of 1 or more.] Is}
5. The conductive polyaniline composition according to 4, which is a sulfosuccinic acid derivative represented by the formula:
6). The conductive polyaniline composition according to any one of 1 to 5, wherein the inorganic acid is hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid.
7). The conductive polyaniline composition according to any one of 1 to 6, wherein the organic solvent is a solvent that is substantially immiscible with water.
8). The conductive polyaniline composition according to any one of 1 to 6, wherein the organic solvent is a water-soluble organic solvent.
9. Furthermore, the electroconductive polyaniline composition in any one of 1-8 containing resin or the precursor of resin.
10. 10. The conductive polyaniline composition according to 9, wherein the resin is a chlorinated polyolefin.
11. The organic solvent is a mixture of a water-immiscible organic solvent and a water-soluble organic solvent, and the mixing ratio (water-immiscible organic solvent: water-soluble organic solvent) is a mass ratio of 99-50: 1-50. The conductive polyaniline composition according to any one of 1 to 10, wherein
12 The water-immiscible organic solvent is selected from aromatic solvents, halogen-containing solvents, ester solvents, ketones having 4 or more carbon atoms, alcohols having 5 or more carbon atoms, and acrylic derivatives.
12. The conductive polyaniline composition according to 11, wherein the water-soluble organic solvent is selected from water-soluble alcohols, water-soluble ketones, water-soluble oxygen-containing ring derivatives, and aprotic polar solvents.
13. Substituted or unsubstituted aniline is polymerized in a first step at a temperature of −10 ° C. to 20 ° C. with an organic acid or a salt thereof, and an inorganic acid or a salt thereof, and further 3 w at a temperature higher than 5 ° C. / M ^{3 A} method for producing a substituted or unsubstituted polyaniline complex doped with an organic acid and an inorganic acid, which is polymerized in the second and subsequent steps with a stirring power of ³ or less.
14 14. The method for producing a polyaniline complex according to 13, wherein the polyaniline complex is produced in a two-phase system of an organic solvent substantially immiscible with water and an aqueous solution.
15. The organic acid or a salt thereof is represented by the following general formula (I ′)
M (XARn) m (I ′)
{Wherein M is a hydrogen atom or an organic or inorganic free radical, X is an acidic group, A is a hydrocarbon group which may contain a substituent, and R is independently- R ¹ , —OR ¹ , —COR ¹ , —COOR ¹ , —CO (COR ¹ ), or —CO (COOR ¹ ) [wherein R ¹ is a hydrocarbon having 4 or more carbon atoms which may contain a substituent. Group, silyl group, alkylsilyl group, — (R ² O) x—R ³ group, or — (OSiR ³ ₂ ) x—OR ³ (R ² is an alkylene group, and R ³ may be the same or different. Is a good hydrocarbon group, x is an integer of 1 or more], n is an integer of 2 or more, and m is the valence of M} or a salt thereof The manufacturing method of the polyaniline composite_body | complex of 13 or 14 which is these.
16. The organic protonic acid represented by the formula (I) or a salt thereof is represented by the following formula (II ′)
M (XCR ⁴ (CR ⁵ ₂ COOR ⁶ ) COOR ⁷ ) _p (II ′)
{In the formula, M is a hydrogen atom or an organic or inorganic free radical; X is an acidic group; and R ⁴ and R ⁵ are each independently a hydrogen atom, a hydrocarbon group, or an R ⁸ ₃ Si— group. (Wherein R ⁸ is a hydrocarbon group, and three R ⁸ may be the same or different), and R ⁶ and R ⁷ are each independently a hydrocarbon group or — (R ⁹ O ) _Q- R ¹⁰ group [wherein R ⁹ is a hydrocarbon group or a silylene group, R ¹⁰ is a hydrogen atom, a hydrocarbon group or R ¹¹ ₃ Si— (R ¹¹ is a hydrocarbon group, R ¹¹ may be the same or different, and q is an integer of 1 or more], p is an valence of M}, or an organic protonic acid or a salt thereof represented by 15 A method for producing a polyaniline complex. 17. The organic protonic acid represented by the formula (II) or a salt thereof is represented by the following formula (III ′)
M (O ₃ SCH (CH ₂ COOR ¹² ) COOR ¹³ ) _m (III ′)
{In the formula, M is a hydrogen atom or an organic or inorganic free radical; R ¹² and R ¹³ are each independently a hydrocarbon group or a — (R ¹⁴ O) _r —R ¹⁵ group [where R ¹⁴ Is a hydrocarbon group or a silylene group, R ¹⁵ is a hydrogen atom, a hydrocarbon group or an R ¹⁶ ₃ Si— group (where R ¹⁶ is a hydrocarbon group, and three R ¹⁶ may be the same or different) And r is an integer of 1 or more], and m is a valence of M}. The method for producing a polyaniline complex according to 16, which is a sulfosuccinic acid derivative.
18. 18. A substituted or unsubstituted polyaniline complex doped with an organic acid and an inorganic acid obtained by the production method according to any one of 13 to 17 above.
19. 19. A process for producing a conductive polyaniline composition comprising reacting a substituted or unsubstituted polyaniline complex doped with an organic acid and an inorganic acid as described in 18 above with a compound having a phenolic hydroxyl group.
20. The electroconductive molded object formed by shape | molding the electroconductive polyaniline composition in any one of said 1-12.
21. 13. A conductive film formed by molding the conductive polyaniline composition according to any one of 1 to 12 above.
22. The surface conductive article formed by apply | coating the electroconductive polyaniline composition in any one of said 1-12 to a base material.
23. 23. The surface conductive article according to 22, wherein the substrate is a resin film.
24. A conductive article obtained by mixing the conductive polyaniline composition according to any one of 1 to 12 above with a base material.
25. A conductive article obtained by electrospinning the conductive polyaniline composition according to any one of 1 to 12 above to a base material.

  ADVANTAGE OF THE INVENTION According to this invention, the novel outstanding polyaniline composite_body | complex, its manufacturing method, a composition and molded object using the same can be provided.

  The conductive polyaniline composition of the present invention comprises an organic solvent, a substituted or unsubstituted polyaniline complex doped with an organic acid and an inorganic acid (hereinafter referred to as polyaniline complex), and a compound having a phenolic hydroxyl group (hereinafter referred to as “polyaniline complex”). A phenolic compound). The polyaniline complex and the phenolic compound are dissolved in an organic solvent.

Here, the sum (a) of the doping rates of the organic acid and the inorganic acid in the polyaniline composite is 0.4 <a <0.6. The sum (a) of the doping ratio of organic acid and inorganic acid in the polyaniline complex is 0.5, which means that one molecule of dopant is doped with respect to two molecules of nitrogen, and this value and the vicinity thereof. , The conductivity is the highest.
The ratio of the doping of the organic acid and the inorganic acid is such that the ratio (b / a) of the doping ratio (b) of the inorganic acid is 0.02 or more in the total doping ratio (a), preferably organic acid: inorganic Acid = 0.98: 0.02-0.90: 0.1.

Here, when the total dope ratio of the organic acid and the inorganic acid is 0.6 or more, the intrinsic conductivity of the conductive composition obtained in the present invention tends to decrease. On the other hand, if it is 0.4 or less, it becomes insoluble in various solvents, resulting in a significant loss of workability such as coating of a substrate.
Further, in order to obtain a conductive composition having a high conductivity, the doping rate of the inorganic acid plays a very important role, and a total doping rate of 0.02 or more is necessary. When the doping rate of the inorganic acid is 0.02 or more of the total doping rate, the effect of adding the phenolic compound, that is, the intermolecular interaction with the phenolic compound is manifested. As a result, the conductive composition having high conductivity Is given.

  The polyaniline complex has a weight average molecular weight (hereinafter referred to as molecular weight) of 20,000 or more and a molecular weight distribution of less than 5.0. If the molecular weight is less than 20,000, the conductivity is lowered. Preferably the molecular weight is 50,000 to 200,000 or more. If the molecular weight distribution is less than 5.0, the conductivity is increased. Preferably molecular weight distribution is 4.0 or less, More preferably, it is 2.0-4.0.

The molecular weight and molecular weight distribution are measured by gel permeation chromatography (GPC), and detailed measurement conditions will be described later in Examples.
The polyaniline complex and the polyaniline composition of the present invention can be produced by the method described below.

Examples of the substituent of the substituted polyaniline in the polyaniline complex include linear or branched hydrocarbon groups such as methyl group, ethyl group, hexyl group and octyl group, alkoxyl groups such as methoxy group and phenoxy group, aryloxy group, CF _And halogen-containing hydrocarbon groups such as ₃ groups.

Examples of suitable organic acids to be doped into the polyaniline complex include the following formula (I)
HXARn (I)
And organic protonic acid (hereinafter referred to as organic protonic acid (I)).

In the above formula (I), X is an acidic group. For example, —SO ₃ ^— group, —PO ₃ ^2- group, —PO ₄ (OH) ^— group, —OPO ₃ ^2- group, —OPO ₂ ( OH) ^- group, -COO ^- group and the like, -SO ₃ ^- group.

  A is a hydrocarbon group which may contain a substituent, for example, a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms, a substituent such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, menthyl and the like. Including optionally substituted cycloalkyl groups, dicyclohexyl groups such as bicyclohexyl, norbornyl, adamantyl or the like or polycycloalkyl groups, phenyl, tosyl, thiophenyl, pyrrolinyl, pyridinyl, furanyl, etc. An aryl group containing an aromatic ring, naphthyl, anthracenyl, fluorenyl, 1,2,3,4-tetrahydronaphthyl, indanyl, quinolinyl, indonyl, etc., may be condensed diaryl group or polyaryl group, alkylaryl group, etc. Is mentioned.

R is each independently —R ¹ , —OR ¹ , —COR ¹ , —COOR ¹ , —CO (COR ¹ ), or —CO (COOR ¹ ). Here, R ¹ may contain a substituent, a hydrocarbon group having 4 or more carbon atoms, a silyl group, an alkylsilyl group, or a — (R ² O) x—R ³ group, — (OSiR ³ ₂ ) x—. OR ³ (R ² is an alkylene group, R ³ is a hydrocarbon group which may be the same or different, and x is an integer of 1 or more). Examples of when R ¹ is a hydrocarbon group include linear or branched butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, pentadecyl, eicosanyl, etc. Can be mentioned.
n is an integer of 2 or more.

As the compound represented by the formula (I), dialkylbenzenesulfonic acid, dialkylnaphthalenesulfonic acid, and a compound represented by the following formula (II) can be preferably used.
HXCR ⁴ (CR ⁵ ₂ COOR ⁶ ) COOR ⁷ (II)

In the above formula (II), X is an acidic group, for example, —SO ₃ ^— group, —PO ₃ ^2- group, —PO ₄ (OH) ^{2 —} group, —OPO ₃ ^2- group, —OPO ₂ ( OH) ^- group, -COO ^- group and the like, -SO ₃ ^- group.

R ⁴ and R ⁵ are each independently a hydrogen atom, a hydrocarbon group or an R ⁸ ₃ Si— group (wherein R ⁸ is a hydrocarbon group, and three R ⁸ may be the same or different). ). Examples of the hydrocarbon group when R ⁴ and R ⁵ are hydrocarbon groups include a linear or branched alkyl group having 1 to 24 carbon atoms, an aryl group containing an aromatic ring, and an alkylaryl group. The hydrocarbon group when R ⁸ is a hydrocarbon group is the same as in the case of R ⁴ and R ⁵ .

R ⁶ and R ⁷ are each independently a hydrocarbon group or — (R ⁹ O) _q —R ¹⁰ group [wherein R ⁹ is a hydrocarbon group or a silylene group, and R ¹⁰ is a hydrogen atom or a hydrocarbon, A group or R ¹¹ ₃ Si— (R ¹¹ is a hydrocarbon group, three R ¹¹ may be the same or different), and q is an integer of 1 or more. The hydrocarbon group in the case where R ⁶ and R ⁷ are hydrocarbon groups is a linear or branched alkyl group having 1 to 24 carbon atoms, preferably 4 or more carbon atoms, an aryl group containing an aromatic ring, or an alkylaryl Specific examples of the hydrocarbon group when R ⁶ and R ⁷ are hydrocarbon groups include, for example, a linear or branched butyl group, pentyl group, hexyl group, octyl group, decyl group Etc.

（式中、Ｘは−ＳＯ_３基等である）で示される基が挙げられる。
上記有機プロトン酸（II）は、下記式（III）で示されるスルホコハク酸誘導体（以下、スルホコハク酸誘導体（III）という）であることがさらに好ましい。
ＨＯ_３ＳＣＨ（ＣＨ_２ＣＯＯＲ^１２）ＣＯＯＲ^１３ （III）In R ⁶ and R ⁷ , when R ⁹ is a hydrocarbon group, the hydrocarbon group includes a linear or branched alkylene group having 1 to 24 carbon atoms, an arylene group containing an aromatic ring, an alkylarylene group, an aryl An alkylene group and the like; The hydrocarbon group in R ⁶ and R ⁷ when R ¹⁰ and R ¹¹ are hydrocarbon groups is the same as in the case of R ⁴ and R ⁵ , and q is 1 to 10. preferable. Specific examples of the case where R ⁶ and R ⁷ are — (R ⁹ O) _n —R ¹⁰ group include, for example,

(Wherein, X is a —SO ₃ group or the like).
The organic protonic acid (II) is more preferably a sulfosuccinic acid derivative represented by the following formula (III) (hereinafter referred to as sulfosuccinic acid derivative (III)).
HO ₃ SCH (CH ₂ COOR ¹² ) COOR ¹³ (III)

R ¹² and R ¹³ are each independently a hydrocarbon group or — (R ¹⁴ O) _r —R ¹⁵ group [wherein R ¹⁴ is a hydrocarbon group or a silylene group, and R ¹⁵ is a hydrogen atom or a hydrocarbon, A group or an R ¹⁶ ₃ Si— group (wherein R ¹⁶ is a hydrocarbon group, three R ¹⁶ may be the same or different), and r is an integer of 1 or more].

The hydrocarbon group when R ¹² and R ¹³ are hydrocarbon groups is the same as R ⁶ and R ⁷ .
In R ¹² and R ¹³ , the hydrocarbon group in the case where R ¹⁴ is a hydrocarbon group is the same as R ⁹ described above. In R ¹² and R ¹³ , the hydrocarbon group in the case where R ¹⁵ and R ¹⁶ are hydrocarbon groups is the same as R ⁴ and R ⁵ described above.
r is preferably from 1 to 10.

Specific examples when R ¹² and R ¹³ are a — (R ¹⁴ O) _q —R ¹⁵ group are the same as those for — (R ⁹ O) _n —R ¹⁰ in R ⁶ and R ⁷ .
The hydrocarbon group in the case where R ¹² and R ¹³ are hydrocarbon groups is the same as R ⁶ and R ⁷ and is preferably a butyl group, a hexyl group, a 2-ethylhexyl group, a decyl group, or the like.

  Examples of inorganic acids doped into the polyaniline composite include hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid.

  The phenolic compound used in the composition of the present invention is not particularly limited, and any compound having an aromatic hydroxyl group can be suitably used without any particular limitation. That is, substituted phenols, polyhydric phenols, bisphenols, biphenols, and polymers having a phenolic hydroxyl group are suitably used according to the purpose. Specifically, phenol, o-, m- or p-cresol, o-, m- or p-ethylphenol, o-, m- or p-propylphenol, o-, m- or p-butylphenol, o -, M- or p-methoxyphenol, o-, m- or p-ethoxyphenol, o-, m- or p-propoxyphenol, o-, m- or p-butoxyphenol o-, m- or p- Nitrophenol, o-, m- or p-cyanophenol, o-, m- or p-chlorophenol, o-, m- or p-brominated phenol, o-, m- or p-fluorinated phenol, o Substitution of phenol derivatives such as-, m- or p-iodinated phenol, salicylic acid, hydroxybenzoic acid, hydroxynaphthalene, etc. Enols; polyhydric phenolic compounds such as catechol and resorcinol, 4,4′-isopropylidenediphenol (Bis-A), 2-methylenebis (4-methylphenol), 4- (2-phenylpropan-2-yl) ) Bisphenols such as benzene-1,3diol, 4,4′dihydroxybiphenol, 4,4′dihydroxybenzophenone, 4,4′dihydroxydiphenyl ether, 4,4′dihydroxydiphenylsulfone and other biphenols and phenol resins, polyphenols, poly Examples thereof include polymer compounds such as (hydroxystyrene).

  In the composition of the present invention, the phenolic compound is present as a dopant, not as a solvent. The fact that the phenolic compound is a dopant means that the molded product produced from the composition of the present invention to which the phenolic compound is added has a very high electrical conductivity compared to the molded product to which this compound is not added, and an organic solvent. After removal, the molded product obtained from the conductive polyaniline composition of the present invention containing a phenolic compound and the molded product obtained from a polyaniline composite containing no phenolic compound have different UV-vis (UV-visible) spectra. It is clear that the phenolic compound remains in the molded product after the organic solvent is removed. This is not limited to the phenolic compounds suitably used in the present invention, and is not limited to solvents such as phenol and cresol as described above, but is generally a solvent such as naphthol and 2-methylenebis (4-methylphenol). It is also clear from the fact that some compounds are not recognized. That is, these phenolic compounds have a strong molecular interaction with the polyaniline complex of the present invention and form a new composition that exhibits high conductivity.

  The molar concentration of the phenolic compound relative to 1 g of the polyaniline complex is preferably in the range of 0.01 mmol / g to 50 mmol / g. If the amount of this compound added is too small, the effect of improving the electrical conductivity may not be obtained. Moreover, when too much, there exists a possibility that the uniformity of a composition may be impaired or it may become a material by which the transparency and the electrical property were impaired by the influence of the excess phenolic compound. In particular, the range is preferably 0.05 mmol / g to 20 mmol / g.

  From the viewpoint of heat resistance, the phenolic compound preferably has two or more aromatic rings, and more preferably has two aromatic rings. The phenolic compound having two or more aromatic rings is not particularly limited as long as it has aromaticity, for example, two or more aromatic rings such as a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, and a pyrrole ring. And having at least one phenolic hydroxyl group can be used.

As such a compound, a compound represented by the following formula (IV) can be preferably used.
Ar-X-Ar '(IV)
[Wherein, X is a single bond, a group containing an oxygen atom, a nitrogen atom, or a group containing a carbon atom, and Ar and Ar ′ are aromatic ring groups, which may be the same or different. Ar and / or Ar ′ has at least one hydroxyl group. Ar and Ar ′ may have one or more substituents selected from the group consisting of a halogen atom, a nitro group, a nitrile group, an amino group, a cyano group, and a carbonyl group. ]

X is a single bond, an oxygen atom, —NH—, —NHCO—, —COO—, —CO—, —COCH ₂ —, —OCO—, —CH ₂ —, —C ₂ H ₄ —, —C ₃ H _6- and the like can be mentioned. From the standpoint of obtaining heat resistance and high electrical conductivity, preferred examples of X include an oxygen atom.
One or two X can be present in the phenolic compound. When two are present, the two Xs may be the same or different. As such, for example, a single bond and -CH 2 as X _- fluorene structure having a like.

Of the substituents on Ar and Ar ′, examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, and an isobutyl group.
Examples of other substituents for Ar and Ar ′ include halogen, amino group, cyano group, nitro group, nitrile group, and carbonyl group.
A plurality of Ar or Ar ′ substituents may be bonded to each other to form a ring. Examples of the ring structure include a cyclohexyl ring, a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, and a pyrrole ring.

Moreover, as a preferable phenolic compound other than the compound of the formula (IV) in which two aromatic rings are bonded via X, a phenolic compound in which a hydroxyl group is added to a polycyclic aromatic ring such as a naphthalene ring or an anthracene ring is used. Can be mentioned. Such a compound is preferable in that it exhibits heat resistance and high conductivity. Examples of such a compound include α-naphthol and β-naphthol.
The phenolic compound containing two or more aromatic rings is preferably a phenolic compound having a melting point of room temperature or higher or a boiling point of 200 ° C. or higher at room temperature. Particularly preferable examples include 2-, 3-, or 4-hydroxybiphenyl, 2-, 3-, or 4-phenoxyphenol, 1- or 2-naphthol, and the like.

  The organic solvent contained in the polyaniline composition may be a solvent in which the organic solvent is not substantially miscible with water (water-immiscible organic solvent) or a water-soluble organic solvent.

  Examples of water-immiscible organic solvents include aromatic solvents such as toluene, xylene, ethylbenzene, tetralin, and styrene derivatives (such as styrene and divinylbenzene), halogen-containing solvents such as chloroform and dichloromethane, ethyl acetate, and butyl acetate. Ester solvents such as methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones having 4 or more carbon atoms, pentanol, benzyl alcohol and other alcohols having 5 or more carbon atoms, methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, etc. An acrylic derivative is mentioned.

  Examples of the water-soluble organic solvent include water-soluble alcohols such as methanol, ethanol, isopropyl alcohol, butanol and 2-methoxyethanol, water-soluble ketones such as acetone and gamma butyrolactone, water-soluble oxygen-containing ring derivatives such as tetrahydrofuran, N-methyl, and the like. Examples include aprotic polar solvents such as pyrrolidone, dimethylformamide, and dimethyl sulfoxide.

The polyaniline complex and phenolic compound of the present invention are soluble in alcohols such as 2-butanol, 2-pentanol, and benzyl alcohol. Alcohol is preferable from the viewpoint of reducing environmental burden unlike toluene.
Further, in using an organic solvent, a mixed organic solvent of a water-immiscible organic solvent and a water-soluble organic solvent is used in a mass ratio of 99 to 50: 1 to 50, whereby the polyaniline complex solution obtained in the present invention is used. When storing, it is preferable in terms of long-term storage because it can prevent generation of gels and the like.

  The ratio of the polyaniline complex in the organic solvent is usually 900 g / L or less, preferably 0.01 to 300 g / L or less, depending on the type of the organic solvent. If the content of the polyaniline complex is too high, the solution state cannot be maintained, and it becomes difficult to handle the molded body, the uniformity of the molded body is impaired, and consequently the electrical properties and mechanical strength of the molded body. , Resulting in a decrease in transparency. On the other hand, if the content of the polyaniline complex is too small, only a very thin film can be produced when the film is formed by the method described later, which may make it difficult to produce a uniform conductive film.

  The polyaniline composition of the present invention is electrically conductive, and the conductivity can be widely controlled depending on the properties of the polyaniline complex and the type and amount of the compound having a phenolic hydroxyl group to be used. However, it is usually 1.0 S / cm or more, preferably 50 S / cm or more, and more preferably 100 S / cm.

Other resins, inorganic materials, curing agents, plasticizers and the like may be added to the polyaniline composition of the present invention depending on the purpose.
Other resins are added for the purpose of, for example, a binder base material, a plasticizer, a matrix base material, and specific examples thereof include, for example, polyolefins such as polyethylene and polypropylene, chlorinated polyolefins, polystyrenes, polyesters, polyamides, polyacetals. , Polycarbonate, polyethylene glycol, polyethylene oxide, polyacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, polyvinyl alcohol and the like. A chlorinated polyolefin is preferred.

  Moreover, you may use the precursor which can form thermosetting resins, such as an epoxy resin, a urethane resin, a phenol resin, with resin instead of resin.

  According to the present invention, a styrene derivative such as styrene or divinylbenzene, or an acrylic derivative such as methyl methacrylate, ethyl methacrylate, or cyclohexyl methacrylate can be used as the soluble organic medium. This is because the organic medium having these reactive functional groups and polyaniline are homogeneously mixed and dissolved, and then the organic medium having these reactive functional groups is reacted by an arbitrary method, whereby various kinds of conductive materials are obtained. It means that a complex is obtained. That is, for example, a thermosetting or UV curable conductive curable resin can be provided according to a required application.

  Inorganic materials are added for the purpose of, for example, improving strength, surface hardness, dimensional stability and other mechanical properties. Specific examples thereof include silica (silicon dioxide), titania (titanium oxide), alumina ( Aluminum oxide) and the like.

  The curing agent is added, for example, for the purpose of improving strength, surface hardness, dimensional stability and other mechanical properties, and specific examples thereof include, for example, thermosetting agents such as phenol resins, acrylate monomers and photopolymerization. Examples thereof include a photo-curing agent using a property initiator.

  The plasticizer is added for the purpose of improving mechanical properties such as tensile strength and bending strength, and specific examples thereof include phthalic acid esters and phosphoric acid esters.

The conductive polyaniline composition of the present invention is produced by reacting with a phenolic compound after producing a substituted or unsubstituted polyaniline complex as follows.
Substituted or unsubstituted aniline is polymerized in a first step at a temperature of −10 ° C. to 20 ° C. together with an organic acid or a salt thereof and an inorganic acid or a salt thereof, and further 3 Polymerization is performed in the second and subsequent steps with a stirring power of / m ³ or less to produce a substituted or unsubstituted polyaniline complex doped with an organic acid and an inorganic acid.

  Preferably, the polymerization temperature in the first stage is −10 ° C. to 20 ° C., and the polymerization temperature in the second stage and thereafter is 15 ° C. to 40 ° C. The polymerization temperature after the second stage is 5 ° C. or higher, preferably 20 to 30 ° C. higher than the polymerization temperature of the first stage. The dope rate can be adjusted by the polymerization temperature after the second stage. That is, when the polymerization temperature is raised, the doping rate approaches the ideal value of 0.5, and the doping rate of the inorganic dopant tends to increase.

Preferably, the first stage stirring power is 50 to 300 w / m ³ . Preferably, the stirring power after the second stage is 0 to ³ w / m ³ . The molecular weight distribution can be adjusted by the stirring power after the second stage. That is, when the stirring power is reduced, the molecular weight distribution tends to be reduced.
In addition, molecular weight can be adjusted by changing the oxidizing agent density | concentration used for superposition | polymerization, and reaction time.

The polymerization time for each stage can be appropriately set. For example, the polymerization time for the first stage is 5 to 25 hours, and the polymerization time for each stage after the second stage is 0.5 to 4 hours.
The number of stages of polymerization of the polyaniline complex is not particularly limited, but can be efficiently produced by two-stage polymerization.
When a polyaniline complex is produced by such multistage polymerization, a polyaniline complex can be produced stably and reproducibly.

  Furthermore, when manufactured using a water-immiscible organic solvent, a polyaniline complex can be manufactured in a two-phase system of a water-immiscible organic solvent and an aqueous solution.

  Furthermore, when manufacturing by the two-phase system of a water-immiscible organic solvent and aqueous solution, surfactant can be added as needed and the reaction rate and a yield improvement can be aimed at. In this case, the surfactant to be used is not particularly limited, and anionic, cationic, and nonionic surfactants are widely and suitably used. Of these, cationic and nonionic surfactants are preferred.

  The addition amount of the organic acid or salt thereof and the inorganic acid or salt thereof with respect to the substituted or unsubstituted aniline can be appropriately set. For example, the organic acid or salt thereof is 1 to 50 mol% with respect to the substituted or unsubstituted aniline. And 10 to 100 mol% of inorganic acid or salt thereof.

The polyaniline complex is polymerized by, for example, a chemical oxidative polymerization method or an electrolytic polymerization method. The organic acid or a salt thereof is preferably an organic protonic acid or a salt thereof represented by the following formula (I ′).
M (XARn) m (I ′)
{Wherein M is a hydrogen atom or an organic or inorganic free radical, X is an acidic group, A is a hydrocarbon group which may contain a substituent, and R is independently- R ¹ , —OR ¹ , —COR ¹ , —COOR ¹ , —CO (COR ¹ ), —CO (COOR ¹ ) [wherein R ¹ is a hydrocarbon group which may contain a substituent having 4 or more carbon atoms. , A silyl group, a — (R ² O) x—R ³ group, or a — (OSiR ³ ₂ ) x—OR ³ group (R ² is an alkylene group, and R ³ may be the same or different hydrocarbon groups. And x is an integer greater than or equal to 1)], n is an integer greater than or equal to 2, and m is the valence of M}

  In the above formula (I ′), M is a hydrogen atom or an organic or inorganic free radical. Examples of the organic free radical include a pyridinium group, an imidazolium group, and an anilinium group, and examples of the inorganic free radical include sodium, lithium, potassium, cesium, ammonium, and the like. m is the valence of M.

X, A, R, and n are the same as in the above formula (I).
As the compound represented by the formula (I ′), dialkylbenzene sulfonic acid, dialkyl naphthalene sulfonic acid, sulfophthalic acid ester, and a compound represented by the following formula (II ′) can be preferably used.
M (XCR ⁴ (CR ⁵ ₂ COOR ⁶ ) COOR ⁷ ) _p (II ′)

In the above formula (II ′), M is the same as in the formula (I ′). X, R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same as in the above formula (II). p is the valence of M.
The organic protonic acid or a salt thereof (II ′) is more preferably a sulfosuccinic acid derivative represented by the following formula (III ′) (hereinafter referred to as sulfosuccinic acid derivative (III ′)).

M (O ₃ SCH (CH ₂ COOR ¹² ) COOR ¹³ ) _m (III ′)
In the above formula (III ′), M and m are the same as in the above formula (I ′). R ¹² and R ¹³ are the same as in the above formula (III).

  After obtaining the polyaniline complex, it is reacted with a phenolic compound. The phenolic compound may be added in a solid state or in a liquid state, or may be added in a state dissolved or suspended in a water-immiscible solvent. Preferably, an appropriate solvent addition method is selected so as to be in a dissolved state even after the addition.

  When the polyaniline complex is produced in a water-immiscible organic solvent, it can be produced by adding a phenolic compound to the polyaniline complex dissolved in the water-immiscible organic solvent.

  A conductive molded body is obtained from the polyaniline composition of the present invention. Specifically, a conductive molded body is obtained by molding the polyaniline composition of the present invention and removing the organic solvent.

When the molded product of the present invention is a film or a film, the thickness is usually 1 mm or less, preferably 10 nm to 50 μm. A film having a thickness in this range is advantageous in that it does not easily crack during film formation and has uniform electrical characteristics.
In particular, when the conductive polyaniline composition of the present invention is formed into a film, a tough and flexible self-supporting conductive film can be obtained. This film can have a tensile elongation of 10% or more at a pulling speed of 1 mm / min.

  A conductive film (surface conductive article) can be produced by applying the conductive polyaniline composition of the present invention to a substrate such as glass, a resin film, a sheet or a nonwoven fabric having a desired shape and removing the organic solvent. .

  As a method for applying the composition to a substrate, known general methods such as a casting method, a spray method, a dip coating method, a doctor blade method, a barcode method, a spin coating method, an electrospinning method, screen printing, and a gravure printing method are used. Can be used.

  In order to remove the organic solvent, the organic solvent may be volatilized by heating. As a method for volatilizing the organic solvent, for example, heating is performed at a temperature of 250 ° C. or less, preferably 50 to 200 ° C. under an air stream, and further, heating is performed under reduced pressure as necessary. The heating temperature and the heating time are not particularly limited and may be appropriately selected depending on the material to be used.

  Moreover, the polyaniline composition of the present invention may be mixed with a base material to form a conductive article. Thermoplastics such as polyolefins such as polyethylene and polypropylene, chlorinated polyolefins, polystyrene, polyester, polyamide, polyacetal, polycarbonate, polyethylene glycol, polyethylene oxide, polyacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, polyvinyl alcohol Examples thereof include thermosetting resins such as resins, epoxy resins, phenol resins, and urethane resins.

Furthermore, the molded article of the present invention can be a self-supporting molded article having no substrate. In the case of a self-supporting molded body, preferably, a molded body having a desired mechanical strength can be obtained when the composition contains the other resin described above.
[Example]

Example 1
[Production of polyaniline complex]
1.8 g of AOT (sodium diisooctylsulfosuccinate) was dissolved in 50 mL of toluene, and the solution was put into a 500 mL separable flask placed under a nitrogen stream, and 1.8 mL of aniline was further added to this solution. Thereafter, 150 mL of 1N hydrochloric acid was added to the solution, and the solution temperature was cooled to 5 ° C.

When the internal temperature of the solution reached 5 ° C., stirring was started with a stirring strength of 180 w / m ³ with a Teflon (registered trademark) anchor blade, and 3.6 g of ammonium persulfate was dissolved in 50 mL of 1N hydrochloric acid. The solution was added dropwise using a dropping funnel over 2 hours. The reaction was carried out while maintaining the internal temperature of the solution at 5 ° C. for 18 hours from the start of dropping. Thereafter, 125 mL of toluene was added, the reaction temperature was increased to 25 ° C. under the condition of a stirring intensity of 3 w / m ³ , and the reaction was continued for 4 hours.

  Thereafter, the aqueous phase separated into two phases by standing was separated, and the toluene phase was washed twice with 50 mL of ion-exchanged water and once with 50 mL of 1N hydrochloric acid to obtain a polyaniline complex toluene solution.

  Some insoluble matter contained in the complex solution was removed with # 5C filter paper, and a toluene solution of the polyaniline complex was recovered. The solution was transferred to an evaporator, heated in a hot water bath at 60 ° C., and reduced in pressure to evaporate volatile components to obtain 1.16 g of a polyaniline complex.

[Characteristics of polyaniline composite and polyaniline composition]
1 g of the obtained polyaniline complex was dissolved again in 20 ml of toluene, and washed with water 5 times in a separatory funnel to completely remove impurities. Thereafter, toluene was evaporated to dryness, the polyaniline complex was recovered and subjected to elemental analysis, and the contents of carbon, hydrogen, nitrogen, sulfur and chlorine were measured. From this measurement, the dope rate of sulfosuccinic acid and chlorine with respect to the polyaniline skeleton was calculated, and the sum was taken as the total dope rate of organic acid and inorganic acid. The results are shown in Tables 1 and 2.

  At the same time, 1 g of the polyaniline complex obtained was taken and redissolved in 20 ml of toluene. This solution was mixed with 40 ml of 1N aqueous sodium hydroxide solution, and the precipitate was collected by filtration. This solid content is dissolved in 0.01 mol LiBr / N-methylpyrrolidone solution, GPC measurement is performed under the conditions of 60 ° C. and a flow rate of 0.35 ml / min, and the molecular weight and molecular weight distribution are determined by the polystyrene (PS) conversion method. (Measurement column: TOSOH TSK-GEL GMHHR-H). The results are shown in Table 2.

  Further, 1 g of the obtained polyaniline complex is dissolved again in 20 ml of toluene to prepare a uniform polyaniline complex solution, and is formed on an ITO (indium tin oxide) substrate by a spin coating method. Intrinsic conductivity was measured. A toluene solution of the polyaniline complex was prepared in the same manner as described above, and 2 ml of m-cresol was further added to obtain a polyaniline composition. The results are shown in Table 2.

  The obtained polyaniline composition solution was formed on an ITO substrate by a spin coating method, and the intrinsic conductivity was measured by a four-terminal method. The results are shown in Table 2.

Example 2
A polyaniline complex was obtained in the same manner as in Example 1 except that the polymerization temperature in the first stage was changed to 0 ° C. in Example 1. Furthermore, using this polyaniline composite, the same procedures and operations as in Example 1 were followed, and the organic acid, inorganic acid dope rate, molecular weight, molecular weight distribution, intrinsic conductivity of the polyaniline composite, and a composition with a phenolic compound The intrinsic conductivity of was measured. The results are shown in Tables 1 and 2.

Example 3
A polyaniline complex was obtained in the same manner as in Example 1 except that the polymerization temperature in the second stage was 10 ° C. in Example 1. Furthermore, using this polyaniline composite, the same procedures and operations as in Example 1 were followed, and the organic acid, inorganic acid dope rate, molecular weight, molecular weight distribution, intrinsic conductivity of the polyaniline composite, and a composition with a phenolic compound The intrinsic conductivity of was measured. The results are shown in Tables 1 and 2.

Example 4
A polyaniline complex was obtained in the same manner as in Example 1 except that the concentration of hydrochloric acid used for polymerization in Example 1 was changed to 0.5N. Furthermore, using this polyaniline composite, the same procedures and operations as in Example 1 were followed, and the organic acid, inorganic acid dope rate, molecular weight, molecular weight distribution, intrinsic conductivity of the polyaniline composite, and a composition with a phenolic compound The intrinsic conductivity of was measured. The results are shown in Tables 1 and 2.

Comparative Example 1
AOT 1.8g was melt | dissolved in toluene 50mL, the solution was put into the 500 mL separable flask put under nitrogen stream, and 1.8 mL aniline was further added to this solution. Thereafter, 150 mL of 1N hydrochloric acid was added to the solution, and the solution temperature was cooled to 5 ° C.
When the internal temperature of the solution reached 5 ° C., stirring was started with a stirring strength of 180 w / m ³ with a Teflon (registered trademark) anchor blade, and 3.6 g of ammonium persulfate was dissolved in 50 mL of 1N hydrochloric acid. The solution was added dropwise using a dropping funnel over 2 hours. The reaction was carried out while maintaining the internal temperature of the solution at 5 ° C. for 18 hours from the start of dropping. Thereafter, the aqueous phase separated into two phases by standing was separated, and the toluene phase was washed twice with 50 mL of ion-exchanged water and once with 50 mL of 1N hydrochloric acid to obtain a polyaniline complex toluene solution.

  Some insoluble matter contained in the complex solution was removed with # 5C filter paper, and a toluene solution of the polyaniline complex was recovered. This solution was transferred to an evaporator, heated in a hot water bath at 60 ° C., and reduced in pressure to evaporate and remove volatile components, whereby 1.05 g of a polyaniline complex was obtained.

  About the obtained polyaniline complex, the intrinsic conductivity, the doping rate, the molecular weight, and the molecular weight distribution were measured in the same manner as in Example 1. Moreover, the intrinsic conductivity of the composition with the phenolic compound was measured. The results are shown in Tables 1 and 2.

Comparative Example 2
AOT 1.8g was melt | dissolved in toluene 50mL, the solution was put into the 500 mL separable flask put under nitrogen stream, and 1.8 mL aniline was further added to this solution. Thereafter, 150 mL of 1N hydrochloric acid was added to the solution, and the solution temperature was cooled to 5 ° C.

When the internal temperature of the solution reached 5 ° C., stirring was started with a stirring strength of 180 w / m ³ with a Teflon (registered trademark) anchor blade, and 3.6 g of ammonium persulfate was dissolved in 50 mL of 1N hydrochloric acid. The solution was added dropwise using a dropping funnel over 2 hours. The reaction was carried out while maintaining the internal temperature of the solution at 5 ° C. for 4 hours from the start of dropping.

  Thereafter, the aqueous phase separated into two phases by standing was separated, and the toluene phase was washed twice with 50 mL of ion-exchanged water and once with 50 mL of 1N hydrochloric acid to obtain a polyaniline complex toluene solution.

  Some insoluble matter contained in the complex solution was removed with # 5C filter paper, and a toluene solution of the polyaniline complex was recovered. The solution was transferred to an evaporator, heated in a hot water bath at 60 ° C., and reduced in pressure to evaporate and remove volatile components to obtain 0.55 g of a polyaniline complex.

  About the obtained polyaniline composite_body | complex, it carried out similarly to Example 1, and measured the dope rate, molecular weight, molecular weight distribution, and intrinsic conductivity. Moreover, the intrinsic conductivity of the composition with the phenolic compound was measured. The results are shown in Tables 1 and 2.

Comparative Example 3
2.7 g of AOT was dissolved in 50 mL of toluene, and the solution was put into a 500 mL separable flask placed in a nitrogen stream, and 1.8 mL of aniline was further added to this solution. Thereafter, 150 mL of 1N hydrochloric acid was added to the solution, and the solution temperature was cooled to 5 ° C.

When the internal temperature of the solution reached 5 ° C., stirring was started with a stirring strength of 180 w / m ³ with a Teflon (registered trademark) anchor blade, and 3.6 g of ammonium persulfate was dissolved in 50 mL of 1N hydrochloric acid. The solution was added dropwise using a dropping funnel over 2 hours. The reaction was carried out while maintaining the internal temperature of the solution at 5 ° C. for 18 hours from the start of dropping. Thereafter, 125 mL of toluene was added, and the reaction temperature was increased to 25 ° C. under the condition of a stirring intensity of 22 w / m ³ , and the reaction was continued for 4 hours.
Thereafter, a polyaniline complex was obtained in the same manner as in Example 1. Furthermore, the dope rate, molecular weight, molecular weight distribution, and intrinsic conductivity were measured by the same procedure and operation as in Example 1. Moreover, the intrinsic conductivity of the composition with the phenolic compound was measured. The results are shown in Tables 1 and 2.

Comparative Example 4
Polymerization of the polyaniline complex was carried out in the same manner as in Example 1 except that the amount of AOT used for polymerization was changed to 0.9 g in Example 1. However, in this case, the polyaniline complex was hardly recovered from the toluene phase side, and most was recovered as an insoluble matter. This insoluble matter was separated by filtration, washed several times with water and dried, and further purified twice by washing with hexane. This was subjected to elemental analysis in the same manner as in Example 1, and the dope rate was measured.
The polyaniline complex obtained at the same time was mixed with a 1N aqueous sodium hydroxide solution in the same manner as in Example 1, and after re-recovery, it was subjected to GPC measurement to measure molecular weight and molecular weight distribution.

  Further, the obtained polyaniline complex was redissolved in toluene in the same manner as in Example 1 and an attempt was made to measure the intrinsic conductivity.

  From Table 2, when a phenolic compound is added to the polyaniline composites in Examples 1 to 4, the intrinsic conductivity is dramatically improved. From Comparative Examples 1 to 4, the effect of adding the phenolic compound is obtained. It is apparent that the polyaniline complex depends on the dope rate, the content of the inorganic dopant, the molecular weight and the molecular weight distribution of the polymer.

Example 5
1 g of the polyaniline complex obtained in Example 1 was dissolved again in 20 ml of toluene to prepare a uniform polyaniline complex solution. Here, 1 g of 2-naphthol was added instead of m-cresol to obtain a polyaniline composition. This solution was formed on an ITO substrate by spin coating, and the intrinsic conductivity was measured by a four-terminal method. The obtained coating film had an intrinsic conductivity of 122 S / cm.

Example 6
A polyaniline composition was obtained in the same manner as in Example 5 except that 1 g of 2-methylenebis (4-methylphenol) was used instead of 2-naphthol in Example 5. This solution was formed on an ITO substrate by spin coating, and the intrinsic conductivity was measured by a four-terminal method. The obtained coating film had an intrinsic conductivity of 76 S / cm.

  From Examples 5 and 6, the role of the phenolic compound in the present invention is not a function as a mere solvent, but a molecular interaction with the polyaniline complex to form a composition having a high intrinsic conductivity. It is clear.

Example 7
The specific conductivity was measured in the same manner as in Example 1 except that 1 g of the polyaniline complex obtained in Example 1 was dissolved in 20 ml of an alcohol solvent. Table 3 shows the solvents used and the intrinsic conductivity obtained.

Example 8
1 g of the polyaniline complex obtained in Example 1 was dissolved again in 20 ml of toluene solution to prepare a polyaniline complex solution, and further 2 ml of m-cresol was added to obtain a polyaniline composition.
This composition was spread on a glass substrate in a range of 14 mm × 52 mm, and dried at 80 ° C. for 30 minutes in an air stream to form a conductive film having a thickness of 16 μm. Using the tensile tester, the obtained conductive film was measured in accordance with DIN 53504-53, with a tensile speed of 1 mm / min. A tensile test was carried out. As a result, the elongation at break was 22%.

Example 9
The polyaniline composition obtained in Example 8 was applied to a glass substrate by a spin coating method, and this substrate was held at 105 ° C. for 500 hours in a nitrogen atmosphere to measure a change in surface resistance value. The results are shown in Table 4.

Example 10
The polyaniline complex obtained in Example 1 was dissolved in toluene to prepare a 5 wt% polyaniline complex solution. To 5 g of this solution, 1.25 g of chlorinated polyethylene resin Super Clone HE-505 (manufactured by Nippon Paper Chemicals Co., Ltd.) was added, and 2 mL of m-cresol was added to obtain a uniform solution to obtain a polyaniline composition.

The composition prepared above was applied to a 0.3 mm thick super pure array sheet (SG-140TC, manufactured by Idemitsu Unitech Co., Ltd.) using a bar coater and dried in an oven at 80 ° C. for 5 minutes to obtain a conductive sheet. . The surface resistance of this sheet was 1.4 × 10 ² Ω / □.
Further, this solution was applied to a glass substrate by a spin coating method, and this substrate was held at 105 ° C. for 500 hours in a nitrogen atmosphere to measure a change in surface resistance value. The results are shown in Table 4.

Example 11
The same operation as in Example 10 was performed except that HE910 (manufactured by Nippon Paper Chemicals Co., Ltd.) was used as the chlorinated polyethylene resin in Example 10 instead of Super Clone HE505, under a nitrogen atmosphere at 105 ° C., The change of the surface resistance value was measured by holding for 500 hours. The results are shown in Table 4.

As shown in Table 4, the resistance stability under high temperature exposure is greatly improved in the polyaniline composition to which chlorinated polyolefin is added.

Example 12
(1) Synthesis of sodium 3,4-bis [(2-ethylhexyl) oxycarbonyl] cyclohexanesulfonate 4-cyclohexene-1,2-dicarboxylic acid di (2-ethylhexyl) ester (manufactured by Tokyo Chemical Industry Co., Ltd.) under an argon gas stream ) 80 g and isopropyl alcohol 900 mL were charged, and a solution of sodium hydrogen sulfite (manufactured by Wako Pure Chemical Industries, Ltd.) 42.3 g in 660 mL water was added. The solution was heated to reflux temperature and stirred at 80-83 ° C. for 16 hours. During this time, 1.66 g of 2,2′-azobis (isobutyronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) was added every hour from the start of reflux to 1 to 5 hours later, then 9 hours and 10 hours later. did. The reaction solution was cooled to room temperature and then concentrated under reduced pressure. The concentrated residue was dissolved in 1 L of an ethyl acetate / hexane mixed solution, 250 g of silica gel was added and stirred, and the solution was separated by filtration. Further, extraction was performed twice from silica gel with 1 L of ethyl acetate / hexane solution, and the filtrates were combined and concentrated under reduced pressure. This concentrated solution was purified by column chromatography (silica gel 1500 g, developing solvent: ethyl acetate / hexane), and the purified product was dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure, whereby 3,4-bis [(2- Ethylhexyl) oxycarbonyl] sodium cyclohexanesulfonate (Na salt of compound A represented by the following formula) was obtained 52.4 g.

(2) Production of polyaniline complex and composition Sodium 3,4-bis [(2-ethylhexyl) oxycarbonyl] cyclohexanesulfonate synthesized in the above (1) instead of 1.8 g of AOT in Example 1. Except for using 0 g, a polyaniline composite was obtained by the same operation and procedure as in Example 1, and the doping rate, molecular weight, molecular weight distribution, and intrinsic conductivity of organic acid and inorganic acid were measured. Moreover, the intrinsic conductivity of the composition with the phenolic compound was measured. The results are shown in Table 5. As shown in Table 5, in the present invention, a highly conductive conductive composition can be obtained even when an organic acid other than sulfosuccinic acid represented by AOT is used.

Example 13
The polyaniline complex obtained in Example 1 was dissolved in chloroform to prepare a 5 wt% polyaniline complex solution. 6 g of polyethylene oxide (Aldrich) having a weight average molecular weight (Mw) of 900,000 was added to 200 g of the solution, and 20 g of m-cresol and 150 g of isopropyl alcohol were added to obtain a uniform solution to obtain a composition.

This solution was electrospun using Nanospider NS LAB 200S (manufactured by Elmarco) at a distance between electrodes of 160 mm, a voltage of 50 kV, a cylinder rotation speed of 3.5 rpm, and a winding speed of 8 cm / min. A composition was obtained. A polypropylene sheet having a thickness of 0.3 mm and a width of 40 cm and a polypropylene nonwoven fabric having a basis weight of 20 g / m ² and a width of 40 cm were used as the base material. The amount of the polyaniline composition attached to the polypropylene sheet and the polypropylene nonwoven fabric was determined by measuring the weight difference before and after electrospinning. As a result, the adhesion amount of the polyaniline composition was 0.4 to 0.8 g / m ² in all cases.

Example 14
The polyaniline complex obtained in Example 1 was dissolved in chloroform to prepare a 5 wt% polyaniline complex solution. 1 g of polyethylene oxide (Aldrich) having a weight average molecular weight (Mw) of 900,000 was added to 410 g of the solution, and 20 g of m-cresol and 210 g of isopropyl alcohol were added to obtain a uniform solution to obtain a composition.

This solution was electrospun using Nanospider NS LAB 200S (manufactured by Elmarco) at a distance between electrodes of 160 mm, a voltage of 73 kV, a cylinder rotation speed of 3 rpm, and a winding speed of 8 cm / min to obtain a filamentous composition having a diameter of 300 nm or less. It was. The base material used was a polypropylene sheet having a thickness of 0.3 mm and a width of 40 cm, a PET sheet having a thickness of 0.1 mm and a width of 40 cm, and a polypropylene nonwoven fabric having a basis weight of 30 g / m ² and a width of 40 cm. The amount of the polyaniline composition attached to the polypropylene sheet, the PET sheet, and the polypropylene nonwoven fabric was determined by measuring the weight difference before and after electrospinning. As a result, the adhesion amount of the polyaniline composition was 0.4 to 0.8 g / m ² in all cases.

Example 15
5 parts by mass of the polyaniline complex obtained in Example 1 was dissolved in 95 parts by mass of chloroform or toluene. To this solution, 10 parts by mass of m-cresol and 1 to 90 parts by mass of various highly polar organic solvents shown in Table 6 were added to prepare a polyaniline composition solution. The obtained polyaniline composition solution was formed on an ITO substrate by spin coating, and the intrinsic conductivity was measured by a four-terminal method. The results shown in Table 6 were obtained.
Further, when the storage stability of each obtained polyaniline composition solution was examined, no gel was observed even after storage for 10 days.

  The polyaniline composite, conductive polyaniline composition, and molded product of the present invention are in the field of power electronics and optoelectronics. Electrostatic / antistatic material, transparent electrode and conductive film material, electroluminescent element material, circuit material, antenna material It can be used for electromagnetic shielding materials, capacitor electrodes / dielectrics / electrolytes, electrode materials for solar cells and secondary batteries, fuel cell separator materials, actuators, various sensor substrates, etc., plating base materials, and rust inhibitors.

Claims (25)

An organic solvent, an organic acid, a substituted or unsubstituted polyaniline complex doped with an inorganic acid, and
A conductive polyaniline composition comprising a compound having a phenolic hydroxyl group,
The sum (a) of the organic acid and inorganic acid doping rates in the polyaniline composite is 0.4 <a <0.6,
Of the total doping rate (a), the proportion (b / a) of the doping rate (b) of the inorganic acid is 0.02 or more,
A conductive polyaniline composition wherein the polyaniline complex has a weight average molecular weight of 20,000 or more and a molecular weight distribution of less than 5.0.   The conductive polyaniline composition according to claim 1, wherein the molar concentration of the compound having a phenolic hydroxyl group with respect to 1 g of the polyaniline complex is in the range of 0.01 mmol / g to 50 mmol / g. The organic acid is represented by the following formula (I)
HXARn (I)
{In the formula, X is an acidic group, A is a hydrocarbon group which may contain a substituent, and R is independently -R ¹ , -OR ¹ , -COR ¹ , -COOR ^1. , —CO (COR ¹ ), or —CO (COOR ¹ ) [wherein R ¹ is a hydrocarbon group, silyl group, — (R ² O) x -R which may contain a substituent having 4 or more carbon atoms. ³ groups or-(OSiR ³ ₂ ) x -OR ³ groups (R ² is an alkylene group, R ³ is a hydrocarbon group which may be the same or different, and x is an integer of 1 or more). And n is an integer greater than or equal to 2}
The conductive polyaniline composition according to claim 1, which is an organic protonic acid represented by the formula: The organic protonic acid represented by the formula (I) is represented by the following formula (II)
HXCR ⁴ (CR ⁵ ₂ COOR ⁶ ) COOR ⁷ (II)
{In the formula, X is an acidic group, R ⁴ and R ⁵ are each independently a hydrogen atom, a hydrocarbon group or an R ⁸ ₃ Si- group (wherein R ⁸ is a hydrocarbon group, Three R ⁸ may be the same or different, and R ⁶ and R ⁷ are each independently a hydrocarbon group or a — (R ⁹ O) _q —R ¹⁰ group [where R ⁹ is carbon A hydrogen group or a silylene group, R ¹⁰ is a hydrogen atom, a hydrocarbon group or R ¹¹ ₃ Si— (R ¹¹ is a hydrocarbon group, and three R ¹¹ may be the same or different); q is an integer greater than or equal to 1]}
The conductive polyaniline composition according to claim 3, which is an organic protonic acid represented by the formula: The organic protonic acid represented by the formula (II) is represented by the following formula (III)
HO ₃ SCH (CH ₂ COOR ¹² ) COOR ¹³ (III)
{Wherein R ¹² and R ¹³ are each independently a hydrocarbon group or — (R ¹⁴ O) _r —R ¹⁵ group [wherein R ¹⁴ is a hydrocarbon group or a silylene group, and R ¹⁵ is hydrogen An atom, a hydrocarbon group, or an R ¹⁶ ₃ Si— group (where R ¹⁶ is a hydrocarbon group, and three R ¹⁶ may be the same or different), and r is an integer of 1 or more.] Is}
The conductive polyaniline composition according to claim 4, which is a sulfosuccinic acid derivative represented by the formula:   The conductive polyaniline composition according to claim 1, wherein the inorganic acid is hydrochloric acid, sulfuric acid, phosphoric acid, or nitric acid.   The conductive polyaniline composition according to claim 1, wherein the organic solvent is a solvent that is substantially immiscible with water.   The conductive polyaniline composition according to claim 1, wherein the organic solvent is a water-soluble organic solvent.   Furthermore, the electroconductive polyaniline composition in any one of Claims 1-8 containing the precursor of resin or resin.   The conductive polyaniline composition according to claim 9, wherein the resin is a chlorinated polyolefin.   The organic solvent is a mixture of a water-immiscible organic solvent and a water-soluble organic solvent, and the mixing ratio (water-immiscible organic solvent: water-soluble organic solvent) is a mass ratio of 99-50: 1-50. The conductive polyaniline composition according to any one of claims 1 to 10. The water-immiscible organic solvent is selected from aromatic solvents, halogen-containing solvents, ester solvents, ketones having 4 or more carbon atoms, alcohols having 5 or more carbon atoms, and acrylic derivatives.
The conductive polyaniline composition according to claim 11, wherein the water-soluble organic solvent is selected from water-soluble alcohols, water-soluble ketones, water-soluble oxygen-containing ring derivatives, and aprotic polar solvents. Substituted or unsubstituted aniline is polymerized in a first step at a temperature of −10 ° C. to 20 ° C. together with an organic acid or a salt thereof and an inorganic acid or a salt thereof, and further 3 / M ^{3 A} method for producing a substituted or unsubstituted polyaniline complex doped with an organic acid and an inorganic acid, which is polymerized in the second and subsequent steps with a stirring power of ³ or less.   The method for producing a polyaniline complex according to claim 13, wherein the polyaniline complex is produced in a two-phase system of an organic solvent substantially immiscible with water and an aqueous solution. The organic acid or a salt thereof is represented by the following general formula (I ′)
M (XARn) m (I ′)
{Where,
M is a hydrogen atom or an organic or inorganic free radical;
X is an acidic group,
A is a hydrocarbon group which may contain a substituent,
R is each independently —R ¹ , —OR ¹ , —COR ¹ , —COOR ¹ , —CO (COR ¹ ), or —CO (COOR ¹ ) [wherein R ¹ may include a substituent. Good hydrocarbon group having 4 or more carbon atoms, silyl group, alkylsilyl group, — (R ² O) x —R ³ group, or — (OSiR ³ ₂ ) x —OR ³ (R ² is an alkylene group, R ³ Are each a hydrocarbon group which may be the same or different, and x is an integer of 1 or more.
n is an integer greater than or equal to 2,
m is the valence of M}
The method for producing a polyaniline complex according to claim 13 or 14, which is an organic protonic acid represented by the formula (1) or a salt thereof. The organic protonic acid represented by the formula (I) or a salt thereof is represented by the following formula (II ′)
M (XCR ⁴ (CR ⁵ ₂ COOR ⁶ ) COOR ⁷ ) _p (II ′)
{Where,
M is a hydrogen atom or an organic or inorganic free radical;
X is an acidic group,
R ⁴ and R ⁵ are each independently a hydrogen atom, a hydrocarbon group or an R ⁸ ₃ Si— group (wherein R ⁸ is a hydrocarbon group, and three R ⁸ may be the same or different). ) And
R ⁶ and R ⁷ are each independently a hydrocarbon group or — (R ⁹ O) _q —R ¹⁰ group [wherein R ⁹ is a hydrocarbon group or a silylene group, and R ¹⁰ is a hydrogen atom or a hydrocarbon, A group or R ¹¹ ₃ Si— (R ¹¹ is a hydrocarbon group, three R ¹¹ may be the same or different), q is an integer of 1 or more], and p is M Is the valence of
The method for producing a polyaniline complex according to claim 15, wherein the organic protonic acid is represented by the formula: The organic protonic acid represented by the formula (II) or a salt thereof is represented by the following formula (III ′)
M (O ₃ SCH (CH ₂ COOR ¹² ) COOR ¹³ ) _m (III ′)
{In the formula, M is a hydrogen atom or an organic or inorganic free radical; R ¹² and R ¹³ are each independently a hydrocarbon group or a — (R ¹⁴ O) _r —R ¹⁵ group [where R ¹⁴ Is a hydrocarbon group or a silylene group, R ¹⁵ is a hydrogen atom, a hydrocarbon group or an R ¹⁶ ₃ Si— group (where R ¹⁶ is a hydrocarbon group, and three R ¹⁶ may be the same or different) And r is an integer of 1 or more], and m is a valence of M}. The method for producing a polyaniline complex according to claim 16.   A substituted or unsubstituted polyaniline complex doped with an organic acid and an inorganic acid obtained by the production method according to claim 13.   A method for producing a conductive polyaniline composition comprising reacting a substituted or unsubstituted polyaniline complex doped with an organic acid and an inorganic acid according to claim 18 with a compound having a phenolic hydroxyl group.   The electroconductive molded object formed by shape | molding the electroconductive polyaniline composition in any one of Claims 1-12.   The electroconductive film formed by shape | molding the electroconductive polyaniline composition in any one of Claims 1-12.   The surface conductive article formed by apply | coating the electroconductive polyaniline composition in any one of Claims 1-12 to a base material.   The surface conductive article according to claim 22, wherein the substrate is a resin film.   The electroconductive article formed by mixing the electroconductive polyaniline composition in any one of Claims 1-12 with a base material.   A conductive article obtained by electrospinning a conductive polyaniline composition according to any one of claims 1 to 12 to a substrate.